CN103501898A - Process for preparing cobalt containing hydrocarbon synthesis catalyst precursor - Google Patents
Process for preparing cobalt containing hydrocarbon synthesis catalyst precursor Download PDFInfo
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- CN103501898A CN103501898A CN201280022128.7A CN201280022128A CN103501898A CN 103501898 A CN103501898 A CN 103501898A CN 201280022128 A CN201280022128 A CN 201280022128A CN 103501898 A CN103501898 A CN 103501898A
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- Prior art keywords
- catalyst
- cobalt
- precursor
- carrier
- calcining
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- 239000010941 cobalt Substances 0.000 title claims abstract description 40
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 39
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 35
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 35
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 32
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 32
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 29
- 239000012018 catalyst precursor Substances 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title abstract description 34
- 239000003054 catalyst Substances 0.000 claims abstract description 167
- 238000001354 calcination Methods 0.000 claims abstract description 56
- 150000001869 cobalt compounds Chemical class 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims description 114
- 239000003795 chemical substances by application Substances 0.000 claims description 41
- 239000007789 gas Substances 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 14
- -1 cobalt hydrocarbon Chemical class 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052622 kaolinite Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000000446 fuel Substances 0.000 claims description 2
- 239000002243 precursor Substances 0.000 description 72
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 58
- 235000013495 cobalt Nutrition 0.000 description 36
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 36
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 36
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 28
- 239000013078 crystal Substances 0.000 description 16
- 230000000694 effects Effects 0.000 description 16
- 229910052710 silicon Inorganic materials 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 239000011159 matrix material Substances 0.000 description 11
- 239000012071 phase Substances 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- 229910000428 cobalt oxide Inorganic materials 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910052726 zirconium Inorganic materials 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000001868 cobalt Chemical class 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- UKGJZDSUJSPAJL-YPUOHESYSA-N (e)-n-[(1r)-1-[3,5-difluoro-4-(methanesulfonamido)phenyl]ethyl]-3-[2-propyl-6-(trifluoromethyl)pyridin-3-yl]prop-2-enamide Chemical compound CCCC1=NC(C(F)(F)F)=CC=C1\C=C\C(=O)N[C@H](C)C1=CC(F)=C(NS(C)(=O)=O)C(F)=C1 UKGJZDSUJSPAJL-YPUOHESYSA-N 0.000 description 1
- WKBPZYKAUNRMKP-UHFFFAOYSA-N 1-[2-(2,4-dichlorophenyl)pentyl]1,2,4-triazole Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(CCC)CN1C=NC=N1 WKBPZYKAUNRMKP-UHFFFAOYSA-N 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000008365 aqueous carrier Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000012809 cooling fluid Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
- B01J37/0244—Coatings comprising several layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
- C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/12—Silica and alumina
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Chemical Kinetics & Catalysis (AREA)
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- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Crystallography & Structural Chemistry (AREA)
Abstract
A process for preparing a cobalt-containing a hydrocarbon synthesis catalyst precursor includes the steps of calcining a loaded catalyst support comprising a catalyst support supporting a cobalt compound. The calcination includes subjecting the loaded catalyst support to heat treatment by heating the loaded catalyst support to a temperature, T, of at least 220 DEG C at a heating rate below 10 DEG C/minute, and effecting gas flow at a space velocity of at least 9m3n/kg cobalt compound/hour over the loaded catalyst support during at least part of the heating. The cobalt-containing hydrocarbon synthesis catalyst precursor is thereby produced.
Description
Technical field
The present invention relates to catalyst.Especially, the present invention relates to, for the preparation of the method containing cobalt hydrocarbon synthesis catalyst precursor, for the preparation of the method for hydrocarbon synthesis catalyst, and comprise the method for producing hydrocarbon with described hydrocarbon synthesis catalyst.
Background technology
The known load type is containing synthetic (the Fischer-Tropsch synthesis of cobalt Fischer-Tropsch, FTS) can prepare by the following method by catalyst: cobalt salt is impregnated on catalyst carrier, and dry through impregnated carrier, then calcine gained drying through impregnated carrier to obtain the FTS catalyst precarsor.Then the reducing catalyst precursor is to obtain comprising the FTS catalyst of the cobalt crystal be dispersed on carrier.
Also known mode of wherein carrying out calcining step can affect the final activity of catalyst.For example, WO2010/011332 discloses a kind of method for preparing the support type cobalt-containing catalyst with homodisperse small crystals.Described method is included on catalyst carrier and deposits cobalt nitrate, then carrier is heated to approximately to 160 ℃ under oxygen containing substantially anhydrous atmosphere with catabolite in the middle of forming.Then calcine this centre catabolite and it is reduced to produce the catalyst with homodisperse small crystals.
Known (for example, by WO2010/011332, being known) is because of the activity containing cobalt FTS catalyst and proportional higher than the cobalt button footpath of 6nm, so estimate that its small crystals and high dispersive will cause catalyst activity to increase.
US6,806,226 disclose cobalt-containing catalyst, and it take all reducible cobalts as formula-unit CoO during calcining step
ah
bmode calcined.Find that the catalyst of preparation has the activity of increase like this.
Also find, in preparing cobalt-containing catalyst, if calcined with the air speed higher than a certain value with lower than the rate of heat addition of a certain value according to the present invention, obtain having the catalyst of small crystals.
Summary of the invention
According to an aspect of the present invention, provide a kind of for the preparation of the method containing cobalt hydrocarbon synthesis catalyst precursor, described method comprises the supported catalyst agent carrier of the catalyst carrier that calcining comprises the Supported Co compound, and described calcining comprises by following process heat-treats the supported catalyst agent carrier:
With the rate of heat addition lower than 10 ℃/minute, the supported catalyst agent carrier is heated to the temperature T of at least 220 ℃; And
During at least a portion of heating, the supported catalyst agent carrier is applied to air speed for 9m at least
3 n/ kg cobalt compound/hour gas flow, thereby produce containing cobalt hydrocarbon synthesis catalyst precursor.
calcining
Calcining supported catalyst agent carrier can comprise makes cobalt compound decompose and/or it is reacted with oxygen.During calcining, cobalt compound for example cobalt nitrate can be converted into cobalt/cobalt oxide, preferably, is selected from CoO, CoO (OH), Co
3o
4, Co
2o
3the perhaps cobalt/cobalt oxide of its one or more of mixture.
Should be understood that the heating during calcining may extend to the temperature higher than 220 ℃, for example high to 230 ℃; Or 250 ℃; Or even 270 ℃.In other words, T can>220 ℃, for example 230 ℃, 250 ℃ or 270 ℃.
The rate of heat addition is preferably lower than 7 ℃/minute, preferably lower than 6 ℃/minute, preferably lower than 3 ℃/minute.
Described air speed during calcining is preferably at least 19m
3 n/ kg cobalt compound/hour, more preferably 29m at least
3 n/ kg cobalt compound/hour.Described air speed can be even up to 98m
3 n/ kg cobalt compound/hour.
In a preferred embodiment of the invention, apply at least 9m at height to 220 ℃ or in even higher than the whole heat treatment of 220 ℃
3 n/ kg cobalt compound/hour air speed.
The gas used during calcining can be any suitable gas, for example inert gas or oxygen-containing gas.Inert gas can be nitrogen.Oxygen-containing gas can be air.
Calcining can be carried out in the fluidized bed calcination unit.Should be understood that the temperature that is heated at least 220 ℃ refers to calcine the bed tempertaure of unit, that is, refer to calcine the temperature of loaded catalyst carrier bed in unit.
catalyst carrier
Catalyst carrier can be the catalyst carrier that is suitable for the precursor compound of supported active catalytic component thereon or active catalyst component.Catalyst carrier preferably is suitable for as the carrier in catalyst, in order to by the oxygenatedchemicals of the synthetic hydrocarbon of hydrogen and carbon monoxide and/or hydrocarbon at least.Preferably, catalyst is Fischer-Tropsch (FT) synthetic catalyst.The FT synthetic catalyst can be used for treating in fixed bed reactors, slurry bed reactor or the method even implemented in fixed fluidized-bed reactor.Preferably, implement described method in three-phase slurry bed FT synthesis reactor.
Catalyst carrier is porous carrier normally, and preferably itself or preformed.The average pore size of carrier is preferably 8 to 50 nanometers, more preferably 10 to 15 nanometers.The carrier pore volume can be 0.1 to 1ml/g catalyst carrier, is preferably 0.3 to 0.9ml/g catalyst carrier.Pre-forming carrier can be particulate vector, and preferably average grain diameter is 1 to 500 micron, more preferably 10 to 250 microns, and also more preferably 45 to 200 microns.
Catalyst carrier can comprise catalyst carrier matrix and optional one or more of modified components.The catalyst carrier matrix can be selected from aluminium oxide (alumina), the silica (SiO of one or more of aluminum oxides (aluminium oxides) form
2), titanium dioxide (TiO
2), magnesia (MgO), zinc oxide (ZnO) and composition thereof.Preferably, carrier matrix is selected from aluminium oxide, the titanium dioxide (TiO of one or more of aluminum oxide forms
2) and silica (SiO
2).More preferably, carrier matrix is the aluminium oxide of one or more of aluminum oxide forms.Carrier matrix can be commercially available product, for example the Puralox(trade name) (being obtained from Sasol Germany GmbH).
Preferably, catalyst carrier comprises one or more of modified components.Particularly in the situation that carrier matrix dissolves in neutrality and/or acidic aqueous solution or carrier matrix, hydro-thermal is corroded to (hydrothermal attack) sensitivity, as mentioned below.
Modified component can comprise the component that causes following one or more of effects:
(i) reduce the dissolving of catalyst carrier in aqueous environments;
(ii) suppress the sensitiveness that catalyst carrier corrodes hydro-thermal (especially in Fischer-Tropsch between synthesis phase);
(iii) increase the pore volume of catalyst carrier;
(iv) increase intensity and/or wear-resistant and/or the wearability of catalyst carrier.
In a preferred embodiment of the invention, modified component reduces the dissolving of catalyst carrier in aqueous environments and/or suppresses the sensitiveness that catalyst carrier corrodes hydro-thermal (especially in Fischer-Tropsch between synthesis phase).Such aqueous environments can comprise acidic aqueous solution and/or neutral aqueous solution, the such environment especially run in aqueous phase catalyst impregnated catalyst preparation process.Hydro-thermal corrode think the synthetic especially Fischer-Tropsch of hydrocarbon between synthesis phase catalyst carrier (for example aluminium oxide) due to the sintering that is exposed to high temperature and water and occurs.
Modified component can comprise following element or consisting of Si, Zr, Co, Ti, Cu, Zn, Mn, Ba, Ni, Na, K, Ca, Sn, Cr, Fe, Li, Ti, Sr, Ga, Sb, V, Hf, Th, Ce, Ge, U, Nb, Ta, W, La and the mixture of two or more thereof.
Modified component can be selected from Si, Zr, Cu, Zn, Mn, Ba, La, W, Ni and one or more of mixtures thereof.Preferably, modified component is selected from Si and Zr.In a preferred embodiment of the invention, modified component is Si.
When modified component is Si, the silicon level of gained catalyst carrier can be at least 0.06 Si atom/square nanometers catalyst carrier, preferred at least 0.13 Si atom/square nanometers catalyst carrier, and more preferably at least 0.26 Si atom/square nanometers catalyst carrier.Preferably, upper limit level is 2.8 Si atom/nm
2catalyst carrier.
In a preferred embodiment of the invention, catalyst carrier comprises the catalyst carrier matrix, described catalyst carrier matrix optionally comprises the modified component that is selected from Si and Zr, and the catalyst carrier matrix is selected from aluminium oxide, the titanium dioxide (TiO of one or more of aluminum oxide forms
2) and silica (SiO
2).Preferably, the catalyst carrier matrix is the aluminium oxide of one or more of aluminum oxide forms, and preferably it comprises and is preferably selected from Si and Zr, preferably the modified component of Si.In a preferred embodiment of the invention, catalyst carrier can be selected from aluminium oxide, the silica (SiO of one or more of aluminum oxide forms
2), titanium dioxide (TiO
2), magnesia (MgO), silica modified aluminium oxide and composition thereof.Preferably, carrier is silica modified aluminium oxide, for example can be obtained from the product of the trade mark Siralox by name of Sasol Germany GmbH.Siralox is the alumina support that comprises spray-dired silica.Silica modified aluminium oxide can be US5, the product described in 045,519, and it is incorporated to this paper by reference.
One or more of aluminum oxides can be selected from the group that comprises gama-alumina, δ-aluminium oxide, θ-aluminium oxide and the mixture of two or more thereof (preferably consisting of).Preferably, described group comprise the mixture of gama-alumina, δ-aluminium oxide and gama-alumina and δ-aluminium oxide or preferably consisting of.Alumina catalyst carrier can be the trade mark Puralox by name that can be obtained from SASOL Germany GmbH, the preferably carrier of Puralox SCCa2/150.Puralox SCCa2/150(trade (brand) name) be the spray-dired alumina support by the compositions of mixtures of gama-alumina and θ-aluminium oxide.
Aluminium oxide preferably can be by formula Al
2o
3.xH
2o(is 0<x<1 wherein) crystalline compounds described.Therefore, the term aluminium oxide does not comprise Al (OH)
3and AlO (OH), but comprise the compound such as gama-alumina, δ-aluminium oxide and θ-aluminium oxide.
the cobalt compound carried on catalyst carrier
Cobalt compound can comprise cobalt salt.
Cobalt compound can comprise organic cobalt compound, but preferably it comprises the inorganic cobalt compound.The inorganic cobalt compound can comprise cobalt salt, preferred cobalt nitrate, and it can be Co (NO especially
3)
2.6H
2o.
The adulterant of reproducibility that can the enhanced activity catalytic component also can be provided on catalyst carrier.Adulterant can be the form of dopant compound, and described dopant compound is the compound that is selected from the metal of the group that comprises palladium (Pd), platinum (Pt), ruthenium (Ru), rhenium (Re) and one or more of mixture thereof.The metal of adulterant (especially palladium metal or platinum) can be 0.01:100 to 3:100 with the mass ratio of cobalt.
In one embodiment of the invention, the cobalt compound carried on catalyst carrier can be by being incorporated into cobalt compound on catalyst carrier and/or in catalyst carrier and preparing.Cobalt compound can be incorporated on catalyst carrier and/or in catalyst carrier by any suitable mode, but preferably it is introduced by dipping.Preferably, catalyst carrier is by forming the catalyst precarsor compound, being flooded by cobalt compound for the mixture of the liquid carrier of catalyst precarsor compound and catalyst carrier.
Liquid carrier can comprise the solvent for the catalyst precarsor compound, and preferably, the catalyst precarsor compound is dissolved in liquid carrier.Liquid carrier can be water.
catalyst precarsor
Cobalt in catalyst precarsor can be the cobalt/cobalt oxide compound comprised containing the oxygen hydroxy compounds.Cobalt/cobalt oxide can be selected from CoO, CoO (OH), Co
3o
4, Co
2o
3or its one or more of mixture.
It is 5 to 70g Co/100g catalyst carriers that catalyst precarsor can comprise load, preferred 20 to 40g Co/100g catalyst carriers, and the more preferably cobalt of 25 to 35g Co/100g catalyst carriers.
The cobalt/cobalt oxide compound can be to be distributed in particle on carrier surface or the form of crystal.
The hydrocarbon synthesis catalyst precursor can be the Fischer-Tropsch catalyst precursor.
catalyst
According to a second aspect of the invention, provide a kind of method for the preparation of hydrocarbon synthesis catalyst, it comprises according to first aspect present invention Kaolinite Preparation of Catalyst precursor, then reduces described catalyst precarsor, to obtain catalyst.
Hydrocarbon synthesis catalyst can be Fischer-Tropsch catalyst.
Catalyst precarsor is preferably processed with the activating catalyst precursor with reducing gas.Preferably, reducing gas is hydrogen or hydrogen-containing gas.Hydrogen-containing gas can and be inertia for active catalyst by hydrogen, and one or more of inert gases form.Hydrogen-containing gas preferably comprises the hydrogen of at least 90 volume %.
Reducing gas can contact with any suitable method with catalyst precarsor.Preferably, so that reducing gas is flowed through, the bed form of grain bed provides catalyst precarsor.Grain bed can be fixed bed, but preferably, it is fluid bed, and preferably, reducing gas serves as the fluidizing agent for the bed of catalyst precarsor particle.
Reduction can, at 0.6 to 1.5 bar (absolute pressure), preferably be carried out under the pressure of 0.8 to 1.3 bar (absolute pressure).Perhaps, pressure can be for 1.5 bar (absolute pressure) to 20 bar (absolute pressure).More preferably, pressure is under about atmospheric pressure.
Reduction is preferably being carried out at the temperature more than 25 ℃, and at this temperature, catalyst precarsor will be reduced to activity form.Preferably, activation higher than 150 ℃ and preferably lower than the temperature of 600 ℃ under carry out, especially in the situation that active catalyst component is cobalt.Preferably, reduction is lower than 500 ℃, preferably lower than carrying out at the temperature of 450 ℃.
Can change temperature between pot-life, and preferably, make temperature increase to above-described maximum temperature.
Preferably control reducing gas and maintain enough low level by flowing of catalyst bed with the pollutant of guaranteeing to produce between reduction period.Reducing gas can recycle, and preferably, processes the reducing gas of recirculation to remove the one or more of pollutants that produce between reduction period.Pollutant can comprise the one or more of of water and ammonia.
Activation can be carried out in one or more step, can change during step one of the rate of heat addition of reducing gas and air speed or both.
In one embodiment of the invention, active catalyst can apply by the following method: introduce the mixture of active catalyst particle and coating media, described coating media is in temperature T
1be the form of melting organic substance down, and at lower temperature T
2(make T
2<T
1) solidify or condense at least one mould; Mould is immersed in cooling fluid at least in part, make organic substance be cooled to temperature T
3, T wherein
3≤ T
2.
hydrocarbon is synthetic
According to a third aspect of the invention we, a kind of hydrocarbon synthesis process is provided, it comprises preparation hydrocarbon synthesis catalyst as above, and under the pressure that cling in the temperature higher than 100 ℃ and at least 10, makes hydrogen and carbon monoxide contact to produce the oxygenatedchemicals of hydrocarbon and optional hydrocarbon with described catalyst.
The contacted temperature of hydrogen and carbon monoxide can be 180 ℃ to 250 ℃, preferably 220 ℃ to 230 ℃.The contacted pressure of hydrogen and carbon monoxide can be 10 bar to 40 bar.
Preferably, hydrocarbon synthesis process is Fischer-Tropsch process, is more preferably the three-phase Fischer-Tropsch process, is more preferably also the slurry bed Fischer-Tropsch process for generation of wax product.
Hydrocarbon synthesis process also can comprise for hydrocarbon and its optional oxygenatedchemicals being converted into to the hydrotreating step of liquid fuel and/or chemicals.
The present invention also extends to the product of producing by the hydrocarbon synthesis process of third aspect present invention.
Further describe the present invention referring now to accompanying drawing and by following non-limiting example.
In the accompanying drawings
Fig. 1 illustrates, for the table 2 and 4 of embodiment 28, the figure of cobalt crystal size and air speed; And
Fig. 2 illustrates, for the table 4 of embodiment 28, and the figure of relative FT activity and air speed.
embodiment 1(is relatively) (C1107/1T)
Studied particulate load type cobalt-based or contained the cobalt fischer-tropsch catalysts precursor, it produces 16g Co/100g Al after activation
2o
3the slurry phase Fischer-Tropsch catalyst that has of the applicant.
The cobalt dipping
The following representative batch for preparing particularly this prereduction catalyst precarsor: with silicon (using the TEOS in ethanol) to from SASOL Germany GmbH(Uberseering40,22297Hamburg, Germany) the Puralox SCCa that pore volume is 0.48ml/g carries out modification, and to make final silicon level be 1.3 quality %Si/g carriers.Flooding (slurry impregnation) containing cobalt nitrate precursor (or supported catalyst agent carrier) by slurry prepares.Use 50.0g H
2o, 39.5gCo (NO
3)
2.6H
2o and 0.0248g Pt (NH
3)
4(NO
3)
2the above-mentioned silica modified gamma-aluminium oxide carrier of solution impregnation 50.0g, and make its under the vacuum of the increase temperature of 60 to 85 ℃ and 260 to 50 millibars dry 6 hours.Calcined precursors as described below.
Calcining dry containing the cobalt nitrate precursor
Dry precursor is loaded in the fluidized bed calcination unit.Under atmospheric pressure, calcined.Air stream is set as 1.97m
3 n/ kg Co (NO
3)
2.6H
2o/ hour.Temperature increases to 250 ℃ and maintain 6 hours under 250 ℃ with 1 ℃/minute by room temperature.Make be cooled to room temperature and unload through the precursor (that is, particulate load containing cobalt fischer-tropsch catalysts precursor) of calcining.
embodiment 2(the present invention) (C1463/1T)
Prepare this embodiment with method similar to Example 1.
Calcining dry containing cobalt nitrate precursor or supported catalyst agent carrier
With the similar method of embodiment 1 method, to calcine the precursor of this embodiment, difference is that air stream is set as 9.87m
3 n/ kg Co (NO
3)
2.6H
2o/ hour.Obtained thus according to particulate load of the present invention containing the cobalt fischer-tropsch catalysts precursor.
embodiment 3(the present invention) (C1462/1T)
Prepare this embodiment with method similar to Example 1.
Calcining dry containing cobalt nitrate precursor or supported catalyst agent carrier
With the similar method of embodiment 1 method, to calcine the precursor of this embodiment, difference is that air stream is set as 19.74m
3 n/ kg Co (NO
3)
2.6H
2o/ hour.
embodiment 4(the present invention) (C1461/1T)
Prepare this embodiment with method similar to Example 1.
Calcining dry containing cobalt nitrate precursor or supported catalyst agent carrier
With the similar method of embodiment 1 method, to calcine the precursor of this embodiment, difference is that air stream is set as 29.61m
3 n/ kg Co (NO
3)
2.6H
2o/ hour.
embodiment 5(the present invention) (C1365/1T)
Prepare this embodiment with method similar to Example 1.
Calcining dry containing cobalt nitrate precursor or supported catalyst agent carrier
With the similar method of embodiment 1 method, to calcine the precursor of this embodiment, difference is that air stream is set as 98.7m
3 n/ kg Co (NO
3)
2.6H
2o/ hour and the rate of heat addition are 0.5 ℃/minute.
embodiment 6(the present invention) (C1466/1P)
The following representative batch for preparing particularly this prereduction catalyst precarsor: with method similar to Example 1, except not adding Si, use is from SASOL Germany GmbH(Uberseering40,22297Hamburg Germany) pore volume be 0.48ml/g Puralox SCCa prepares 16g Co/100gAl
2o
3catalyst precarsor.
Calcining dry containing cobalt nitrate precursor or supported catalyst agent carrier
Calcine the precursor of this embodiment with method similar to Example 1, difference is that air stream is set as 9.87m
3 n/ kg Co (NO
3)
2.6H
2o/ hour.
embodiment 7(the present invention) (C1465/1P)
Prepare this embodiment with method similar to Example 6.
Calcining dry containing cobalt nitrate precursor or supported catalyst agent carrier
With the similar method of embodiment 1 method, to calcine the precursor of this embodiment, difference is that air stream is set as 19.74m
3 n/ kg Co (NO
3)
2.6H
2o/ hour.
embodiment 8(the present invention) (C1464/1P)
Prepare this embodiment with method similar to Example 6.
Calcining dry containing cobalt nitrate precursor or supported catalyst agent carrier
With the similar method of embodiment 1 method, to calcine the precursor of this embodiment, difference is that air stream is set as 29.6m
3 n/ kg Co (NO
3)
2.6H
2o/ hour.
embodiment 9(the present invention) (C1456/1M)
The following representative batch for preparing particularly this prereduction catalyst precarsor: the single silicic acid of use is to from SASOL Germany GmbH(Uberseering40,22297Hamburg, Germany) the Puralox SCCa that pore volume is 0.48ml/g carries out modification and its Si load that comprises 1.6m%.With method Kaolinite Preparation of Catalyst precursor embodiment similar to Example 1.
Calcining dry containing cobalt nitrate precursor or supported catalyst agent carrier
Calcine the precursor of this embodiment with method similar to Example 1, difference is that air stream is set as 9.87m
3 n/ kg Co (NO
3)
2.6H
2o/ hour.
embodiment 10(the present invention) (C1457/1M)
Prepare this embodiment with method similar to Example 9.
Calcining dry containing cobalt nitrate precursor or supported catalyst agent carrier
With the similar method of embodiment 1 method, to calcine the precursor of this embodiment, difference is that air stream is set as 19.74m
3 n/ kg Co (NO
3)
2.6H
2o/ hour.
embodiment 11(the present invention) (C1458/1M)
Prepare this embodiment with method similar to Example 9.
Calcining dry containing cobalt nitrate precursor or supported catalyst agent carrier
With the similar method of embodiment 1 method, to calcine the precursor of this embodiment, difference is that air stream is set as 29.61m
3 n/ kg Co (NO
3)
2.6H
2o/ hour.
embodiment 12(the present invention) (C1428/1S)
The following representative batch for preparing particularly this prereduction catalyst precarsor: the single silicic acid of use is to from SASOL Germany GmbH(Uberseering40,22297Hamburg, Germany) the Puralox SCCa that pore volume is 0.48ml/g carries out modification and its Si load that comprises 1.9m%.With method Kaolinite Preparation of Catalyst precursor embodiment similar to Example 1.
Calcining dry containing cobalt nitrate precursor or supported catalyst agent carrier
With the similar method of embodiment 1 method, to calcine the precursor of this embodiment, difference is that air stream is set as 98.7m
3 n/ kg Co (NO
3)
2.6H
2o/ hour and the rate of heat addition are set as 0.5 ℃/minute.
embodiment 13(is relatively) (C1429/1S)
Prepare this embodiment with method similar to Example 12.
Calcining dry containing cobalt nitrate precursor or supported catalyst agent carrier
With the similar method of embodiment 1 method, to calcine the precursor of this embodiment, difference is that air stream is set as 3.95m
3 n/ kg Co (NO
3)
2.6H
2o/ hour.
embodiment 14(the present invention) (C1453/1S)
Prepare this embodiment with method similar to Example 12.
Calcining dry containing cobalt nitrate precursor or supported catalyst agent carrier
With the similar method of embodiment 1 method, to calcine the precursor of this embodiment, difference is that air stream is set as 9.87m
3 n/ kg Co (NO
3)
2.6H
2o/ hour.
embodiment 15(the present invention) (C1454/1S)
Prepare this embodiment with method similar to Example 12.
Calcining dry containing cobalt nitrate precursor or supported catalyst agent carrier
With the similar method of embodiment 1 method, to calcine the precursor of this embodiment, difference is that air stream is set as 19.74m
3 n/ kg Co (NO
3)
2.6H
2o/ hour.
embodiment 16(the present invention) (C1455/1S)
Prepare this embodiment with method similar to Example 12.
Calcining dry containing cobalt nitrate precursor or supported catalyst agent carrier
With the similar method of embodiment 1 method, to calcine the precursor of this embodiment, difference is that air stream is set as 29.61m
3 n/ kg Co (NO
3)
2.6H
2o/ hour.
embodiment 17(the present invention) (C1439/1S)
Prepare this embodiment with method similar to Example 12.
Calcining dry containing cobalt nitrate precursor or supported catalyst agent carrier
With the similar method of embodiment 1 method, to calcine the precursor of this embodiment, difference is that air stream is set as 98.7m
3 n/ kg Co (NO
3)
2.6H
2o/ hour.
embodiment 18(is relatively) (C742/1T)
Studied particulate load type cobalt-based Fisher-Tropsch synthesis catalyst precursor, it produces 16gCo/100g Al after activation
2o
3the slurry phase Fischer-Tropsch catalyst that has of the applicant.
Cobalt floods to obtain having the precursor of 16g Co/100g carrier
The following representative batch for preparing particularly this prereduction catalyst precarsor: with silicon to from SASOL Germany GmbH(Uberseering40,22297Hamburg, Germany) the Puralox SCCa that pore volume is 0.48ml/g carries out modification, and to make final silicon level be 0 to 1.9 quality %Si/g carrier.By slurry, flood to prepare containing the cobalt nitrate precursor.With 15kg distilled water, 11.9kg Co (NO
3)
2.6H
2o and 7.44g Pt (NH
3)
4(NO
3)
2the above-mentioned silica modified gamma-aluminium oxide carrier of solution impregnation 15kg.The temperature of this slurry is increased to 60 ℃, then applies the 20kPa(absolute pressure) pressure.During first 3 hours of drying steps, slowly increase temperature and reached 95 ℃ after 3 hours.After 3 hours by pressure decreased to 3 to the 15kPa(absolute pressure), and use when wetting in the early stage 2.5m%/hour rate of drying.Complete dipping and drying steps cost 9 hours, unload the cobalt nitrate precursor that contains of treated not calcining get off afterwards.This precursor of calcining as described below:
In the Torbed(trade (brand) name) in fluidized-bed reactor by will being loaded into feed hopper containing cobalt nitrate precursor batch, calcine not calcining containing the cobalt nitrate precursor.The Temperature Setting of Torbed reactor is 270 ℃, and air stream is set as 75m
3.h
-1, and the vibra feeder Speed Setting is 10kg.h
-1.After temperature stabilization, open the valve that leads to vibra feeder and by vibration, cobalt nitrate precursor (at room temperature) be supplied in the Torbed reactor.The rate of heat addition of precursor is 77 ℃/minute, is heated to 255 ℃, with hourly space velocity, is 20m
3 n/ kg Co (NO
3)
2.6H
2o/ hour.Process precursor approximately 14 minutes in the Torbed reactor afterwards, make temperature increase to 270 ℃ by 255 ℃ simultaneously, the rate of heat addition is that 1.1 ℃/minute and air speed are 20m
3 n/ kg Co (NO
3)
2.6H
2o/ hour.Cobalt oxide precursor or cobalt-based Fisher-Tropsch synthesis catalyst precursor are unloaded from reactor hopper and cyclone hopper.
Carry out cobalt dipping and precursor calcining in testing equipment (pilot plant).When in all cases, supported catalyst agent carrier (or treated not calcining containing the cobalt nitrate precursor) is in the feed hopper that is loaded into the Torbed reactor, it is the temperature of testing equipment.According to season and weather, the testing equipment temperature is in the scope of 4 ℃ to 30 ℃, and its temperature is called " room temperature " hereinbefore.
embodiment 19(is relatively) (C1675/1S)
Prepare this embodiment with method similar to Example 12.
Calcining dry containing cobalt nitrate precursor or supported catalyst agent carrier
With the similar method of embodiment 1 method, to calcine the precursor of this embodiment, difference is that air stream is set as 4.0m
3 n/ kg Co (NO
3)
2.6H
2o/ hour and the rate of heat addition are 4.3 ℃/minute.
embodiment 20(the present invention) (C1676/1S)
Prepare this embodiment with method similar to Example 12.
Calcining dry containing cobalt nitrate precursor or supported catalyst agent carrier
With the similar method of embodiment 1 method, to calcine the precursor of this embodiment, difference is that air stream is set as 10.0m
3 n/ kg Co (NO
3)
2.6H
2o/ hour and the rate of heat addition are 5 ℃/minute.
embodiment 21(the present invention) (C1674/1S)
Prepare this embodiment with method similar to Example 12.
Calcining dry containing cobalt nitrate precursor or supported catalyst agent carrier
With the similar method of embodiment 1 method, to calcine the precursor of this embodiment, difference is that air stream is set as 20.0m
3 n/ kg Co (NO
3)
2.6H
2o/ hour and the rate of heat addition are 4.5 ℃/minute.
embodiment 22(the present invention) (C1673/1S)
Prepare this embodiment with method similar to Example 12.
Calcining dry containing cobalt nitrate precursor or supported catalyst agent carrier
With the similar method of embodiment 1 method, to calcine the precursor of this embodiment, difference is that air stream is set as 100.0m
3 n/ kg Co (NO
3)
2.6H
2o/ hour and the rate of heat addition are 4.7 ℃/minute.
embodiment 23(is relatively) (C1751/1T)
Prepare this embodiment with method similar to Example 1.
Calcining dry containing cobalt nitrate precursor or supported catalyst agent carrier
At air stream, be 4.0m
3 n/ kg Co (NO
3)
2.6H
2in the situation that O/ hour and the rate of heat addition are 5.5 ℃/minute, with the similar method of embodiment 1 method, to calcine the precursor of this embodiment.
embodiment 24(the present invention) (C1750/1T)
Prepare this embodiment with method similar to Example 1.
Calcining dry containing cobalt nitrate precursor or supported catalyst agent carrier
With the similar method of embodiment 1 method, to calcine the precursor of this embodiment, difference is that air stream is set as 10.0m
3 n/ kg Co (NO
3)
2.6H
2o/ hour and the rate of heat addition are 5 ℃/minute.
embodiment 25(the present invention) (C1749/1T)
Prepare this embodiment with method similar to Example 1.
Calcining dry containing cobalt nitrate precursor or supported catalyst agent carrier
With the similar method of embodiment 1 method, to calcine the precursor of this embodiment, difference is that air stream is set as 20.0m
3 n/ kg Co (NO
3)
2.6H
2o/ hour and the rate of heat addition are 5 ℃/minute.
embodiment 26(the present invention) (C1748/1T)
Prepare this embodiment with method similar to Example 1.
Calcining dry containing cobalt nitrate precursor or supported catalyst agent carrier
With the similar method of embodiment 1 method, to calcine the precursor of this embodiment, difference is that air stream is set as 100.0m
3 n/ kg Co (NO
3)
2.6H
2o/ hour and the rate of heat addition are 6 ℃/minute.
embodiment 27(the present invention) (C1878/1S)
Prepare this embodiment with method similar to Example 12.
Calcining dry containing cobalt nitrate precursor or supported catalyst agent carrier
With the similar method of embodiment 1 method, to calcine the precursor of this embodiment, difference is that air stream is set as 10m
3 n/ kg Co (NO
3)
2.6H
2o/ hour and the rate of heat addition are 8.6 ℃/minute.
embodiment 28(XRD analyzes)
Make the sample through calcining in embodiment 1 to 27 carry out as follows powder x-ray diffraction analysis:
Sample is filled in the stainless steel specimen holder.The multi-functional diffractometer of Philip X ' Pert Pro (XRD-2 system) is for being analyzed.Instrument is set as follows:
Tube voltage: 40kV
Tube current: 40mA
Source: cobalt (wavelength 1.78897
)
Suo Le slit: 0.04 rad
Bundle mask: 10mm
Automatic divergent slit cascade unit: 10mm
Anti-scatter slit: 2 °
Wave filter: iron
Detector: X ' Celerator
Scanning starts: 5 ° of 2 θ
Be scanned up to: 105 ° of 2 θ
Step-length: 0.0167 ° of 2 θ
Every step time: 150s
Duration scanning: 2 hours
X ' Pert HighScore Plus software is for the identification of the crystalline phase existed in sample.Topas is for being used the basic parameter method to carry out quantitative phase analysis.The syntype refinement technology is for determining the average crystalline size.Absorption of sample stuck-at-１ 0cm
-1.
The average crystalline size is listed in table 1,2,3,4,5 and 6.
Table 1: consist of 16gCo/0.025gPt/0gSi/100gAl
2o
3the Co of sample
3o
4crystal size
Table 2: consist of 16gCo/0.025gPt/1.3gSi/100gAl
2o
3the Co of sample
3o
4crystal size
Table 3: consist of 16gCo/0.025gPt/1.6gSi/100gAl
2o
3the Co of sample
3o
4crystal size
Table 4: consist of 16gCo/0.025gPt/1.9gSi/100gAl
2o
3the Co of sample
3o
4crystal size and relative FT activity
* data error is 5%.The FT activity means with respect to embodiment 13.
Table 5: consist of 16gCo/0.025gPt/1.9gSi/100gAl
2o
3the Co of sample
3o
4crystal size
Table 6: consist of 16gCo/0.025gPt/1.3gSi/100gAl
2o
3the Co of sample
3o
4crystal size
Table 2 and 4 data also are shown in Fig. 1.By Fig. 1, can be clear that, for according to the present invention, (that is, using and surpass 9m
3 n/ kg Co (NO
3)
2.6H
2the air speed of O/ hour, simultaneously the rate of heat addition is less than 10 ℃/minute) catalyst for preparing, the cobalt crystalline size is less.Less cobalt crystal will provide higher FT activity and provide thus better FT performance.
Table 5 and 6 illustrates, and when using that approximately the rate of heat addition of 5 ℃/minute replaces 1 ℃/minute, uses and surpasses 9Nm
3air/kg Co (NO
3)
2.6H
2the air speed of O/ hour has also obtained less cobalt crystal.
embodiment 29
In the high flux fixed bed reactors, embodiment 13,14,15 and 17 is carried out to the Fischer-Tropsch active testing.At first reactor assembly is purified with argon gas.
Under atmospheric pressure, in fixed bed reactors, use 2000ml hydrogen/ml catalyst/hour H
2the stream in-situ reducing is through the precursor of calcining, and makes catalyst precarsor increase to 425 ℃ with the speed of 1 ℃/minute by room temperature.Maintain 10 hours under 425 ℃ after, under hydrogen, make reactor be cooled to 190 ℃.With argon gas, reactor is forced into to 15 bar under 190 ℃
a.
Use the 35000ml/ml catalyst/hour the synthesis gas air speed to start Fischer-Tropsch synthetic, simultaneously common for feedwater to reach the steam of 3 bar in the entrance flow of feed gas.After 30 minutes, with the rate of heat addition of 0.25 ℃/minute, make temperature of reactor increase to 230 ℃.Reach after 230 ℃, adjust air-flow and water and add to reach 22% to 25% CO conversion ratio.
The Fischer-Tropsch activity data means and is shown in Table 4 with respect to embodiment 13.Activity data also is presented in Fig. 2.By these data, can be found out, as the SV>9Nm increased
3air/kgCo (NO
3)
2.6H
2when O/ hour (making the rate of heat addition maintain lower than 10 ℃/minute), strengthened the FT activity simultaneously.
embodiment 30
By commercially available Saturn DigiSizer
tM5200 particle diameters of analyzing catalyst precarsor sample after calcining step distribute.Embodiment 15,18 and 27 is carried out to this operation.
The percentage that is less than the fine material of 45 microns in catalyst is presented in table 7.
Table 7: for embodiment 15 and 18, particulate in catalyst precarsor (%) and Co
3o
4crystalline size
percentage
As can be seen from Table 7, for example, if method for calcinating adopts high-speed (, 20Nm
3air/kgCo (NO
3)
2.6H
2o/ hour, embodiment 15,18 and 27), it causes relatively little cobalt oxide crystal (that is, to be respectively 112,88 and
), and the catalyst that obtains thus having high FT activity.But, for example, if (use the too high rate of heat addition, in embodiment 18 77 ℃/minute), it causes catalyst to break (, the particulate that is less than 45 microns is 12.4%), and the rate of heat addition is maintained enough lowly prevented that catalyst from breaking, but still guaranteed little cobalt crystalline size and high FT activity.
Claims (14)
1. one kind for the preparation of containing the method for cobalt hydrocarbon synthesis catalyst precursor, described method comprises the supported catalyst agent carrier of the catalyst carrier that calcining comprises the Supported Co compound, and described calcining comprises by following process heat-treats described supported catalyst agent carrier:
With the rate of heat addition lower than 10 ℃/minute, described supported catalyst agent carrier is heated to the temperature T of at least 220 ℃; And
During at least a portion of described heating, described supported catalyst agent carrier is applied to air speed for 9m at least
3 n/ kg cobalt compound/hour air-flow, thereby produce described containing cobalt hydrocarbon synthesis catalyst precursor.
2. method according to claim 1, wherein, at described during Heat Treatment, the temperature T that described supported catalyst agent carrier is heated to is approximately 250 ℃.
3. according to claim 1 or method claimed in claim 2, wherein, at described during Heat Treatment, the described rate of heat addition is lower than 6 ℃/minute.
4. the air speed of the described air-flow wherein during described at least a portion of described heating, described supported catalyst agent carrier applied according to the method in any one of claims 1 to 3, is 19m at least
3 n/ kg cobalt compound.
5. method according to claim 4, the air speed of the described air-flow wherein during described at least a portion of described heating, described supported catalyst agent carrier applied is 29m at least
3 n/ kg cobalt compound.
6. method according to claim 5, the air speed of the described air-flow wherein during described at least a portion of described heating, described supported catalyst agent carrier applied is for being up to 98m
3 n/ kg cobalt compound.
7. according to the described method of any one in claim 1 to 6, wherein at height, to the whole described heat treatment of described temperature T, apply at least 9m
3 nthe described air speed of/kg cobalt compound.
8. according to the described method of any one in claim 1 to 7, the gas used during wherein said calcining is air.
9. according to the described method of any one in claim 1 to 8, wherein said calcining is carried out in the fluidized bed calcination unit.
10. the method for the preparation of hydrocarbon synthesis catalyst, it comprises according to any one in claim 1 to 9 and carrys out the Kaolinite Preparation of Catalyst precursor, then reduces described catalyst precarsor, to obtain described catalyst.
11. method according to claim 10, wherein said hydrocarbon synthesis catalyst is Fischer-Tropsch catalyst.
A 12. hydrocarbon synthesis process, it comprises according to claim 10 or the described hydrocarbon synthesis catalyst for preparing of claim 11, and under the pressure of the temperature higher than 100 ℃ and at least 10 bar, hydrogen and carbon monoxide are contacted with described catalyst, with the oxygenatedchemicals of generation hydrocarbon and optional hydrocarbon.
13. method according to claim 12, it comprises for described hydrocarbon and its optional oxygenatedchemicals being converted into to the hydrotreating step of liquid fuel and/or chemicals.
14. by the product according to claim 12 or the described hydrocarbon synthesis process production of claim 13.
Applications Claiming Priority (3)
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|---|---|---|---|
| ZA2011/03330 | 2011-05-06 | ||
| ZA201103330 | 2011-05-06 | ||
| PCT/IB2012/052070 WO2012153218A1 (en) | 2011-05-06 | 2012-04-25 | Process for preparing a cobalt - containing hydrocarbon synthesis catalyst precursor |
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| EP (1) | EP2704828B1 (en) |
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| CA (1) | CA2833964C (en) |
| MY (1) | MY165448A (en) |
| PE (1) | PE20140449A1 (en) |
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| CN103501898B (en) | 2011-05-06 | 2016-01-20 | 沙索技术有限公司 | For the preparation of the method containing cobalt hydrocarbon synthesis catalyst precursor |
| RU2710375C2 (en) | 2014-12-19 | 2019-12-26 | Шелл Интернэшнл Рисерч Маатсхаппий Б.В. | Method of catalyst preparation |
| BR112017017809B1 (en) * | 2015-02-25 | 2022-12-20 | Sasol Technology (Pty) Limited | COBALT CONTAINING CATALYST COMPOSITION, PROCESS FOR PREPARING A COBALT CONTAINING CATALYST, PROCESS FOR PREPARING A COBALT CONTAINING CATALYST PRECURSOR AND HYDROCARBON SYNTHESIS PROCESS |
| CA3122220A1 (en) | 2018-12-10 | 2020-06-18 | Sasol South Africa Limited | Process for preparing a cobalt-containing catalyst precursor and process for hydrocarbon synthesis |
| GB201903502D0 (en) * | 2019-03-14 | 2019-05-01 | Johnson Matthey Plc | Cobalt catalysts and precursors therefor |
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| WO2001039882A1 (en) * | 1999-12-01 | 2001-06-07 | Sasol Technology (Proprietary) Limited | Cobalt catalysts |
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| US4605676A (en) * | 1981-10-13 | 1986-08-12 | Chevron Research Company | Synthesis gas conversion using ROR-activated catalyst |
| DE3839580C1 (en) | 1988-11-24 | 1990-07-05 | Condea Chemie Gmbh, 2212 Brunsbuettel, De | |
| US5292705A (en) * | 1992-09-24 | 1994-03-08 | Exxon Research & Engineering Co. | Activation of hydrocarbon synthesis catalyst |
| ITMI20010478A1 (en) * | 2001-03-08 | 2002-09-08 | Inst Francais Du Petrole | COBALT CATALYST AND ITS USE IN THE FISCHER-TROPSCH PROCESS |
| GB0704003D0 (en) * | 2007-03-01 | 2007-04-11 | Oxford Catalysts | Promoted carbide-based fischer-tropsch catalyst, method for its preparation and uses thereof |
| JP5284346B2 (en) * | 2007-05-04 | 2013-09-11 | サソール テクノロジー（プロプライエタリー）リミテッド | catalyst |
| US8148292B2 (en) | 2008-07-25 | 2012-04-03 | Exxonmobil Research And Engineering Company | Preparation of high activity cobalt catalysts, the catalysts and their use |
| CN103501898B (en) | 2011-05-06 | 2016-01-20 | 沙索技术有限公司 | For the preparation of the method containing cobalt hydrocarbon synthesis catalyst precursor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001039882A1 (en) * | 1999-12-01 | 2001-06-07 | Sasol Technology (Proprietary) Limited | Cobalt catalysts |
| US20050245623A1 (en) * | 2004-04-26 | 2005-11-03 | Sasol Technology (Proprietary) Limited | Catalysts |
| WO2009127990A1 (en) * | 2008-04-15 | 2009-10-22 | Sasol Technology (Proprietary) Limited | Catalysts |
| WO2010097754A2 (en) * | 2009-02-26 | 2010-09-02 | Sasol Technology (Proprietary) Limited | Catalysts |
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| AP2013007246A0 (en) | 2013-11-30 |
| EP2704828B1 (en) | 2021-05-26 |
| PE20140449A1 (en) | 2014-04-15 |
| RU2013154310A (en) | 2015-06-20 |
| BR112013028495B1 (en) | 2019-12-03 |
| CN103501898B (en) | 2016-01-20 |
| US9205409B2 (en) | 2015-12-08 |
| EP2704828A1 (en) | 2014-03-12 |
| NZ617768A (en) | 2015-03-27 |
| RU2591702C2 (en) | 2016-07-20 |
| AR086275A1 (en) | 2013-12-04 |
| MY165448A (en) | 2018-03-22 |
| AP3921A (en) | 2016-12-03 |
| AU2012252073A1 (en) | 2013-12-05 |
| AU2012252073B2 (en) | 2016-07-14 |
| ZA201308535B (en) | 2015-01-28 |
| JP2014514153A (en) | 2014-06-19 |
| CA2833964A1 (en) | 2012-11-15 |
| US20140080929A1 (en) | 2014-03-20 |
| JP5956562B2 (en) | 2016-07-27 |
| WO2012153218A1 (en) | 2012-11-15 |
| CA2833964C (en) | 2019-07-02 |
| BR112013028495A2 (en) | 2018-04-03 |
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